Manufacture of sulpho-halogenated aliphatic monoesters



Patented Oct. 24, 1944 MANUFACTURE OF SULPHO-HALOGENATED ALIPHATICMONOESTERS Herschel G. Smith, Wallingford, and Troy L.

Cantrell, Lansdowne, Pa., and John G. Peters, Audubon, N. J., assignorsto Gulf Oil Corporation, Pittsburgh, Pa., a corporation of PennsylvaniaNo Drawing. Application September 25, 1942,

Serial No. 459,718

13 Qlaims.

This invention relates to the manufacture of sulpho-halogenatedaliphatic monoesters and compositions containing the same.

In particular, it relates to the manufacture of syntheticsulpho-chlorinated-monoesters of fatty acids and compositions containingthe same, especially compounded lubricants comprising a major amount oflubricating oil and a minor amount of such sulpho-chlorinatedmonoesters, the compounded lubricants having many advantageousproperties and being useful for various purposes, particularly inlubricating metal surfaces under ordinary and higher pressures; all asmore fully hereinafter set forth and as claimed.

More specifically, this invention is directed to new and improvedmethods of making sulphochlorinated-monoesters from glycerides ofunsaturated fatty acids, such as lard oil and other fatty oils, withrecovery of glycerine as a valuable byproduct.

Inourimprovedmethods, fatty oils or glycerides containing unsaturatedfatty acids are reacted with sulphur halogen compounds, advantageous lysulphur chlorides, to form sulpho-halogen addition products and thesulpho-halogenated oils or glycerides are converted intosulpho-halogenated monoesters by reaction with a monohydric alcoholadvantageously in the presence of a catalyst such as concentratedsulphuric acid; the sulpho-halogenated glycerides being completelydecomposed and the glycerine being liberated by alcoholysis of thesulpho-halogenated fatty glycerides.

The sulpho-halogenated monoesters so obtained are separated from theglycerine. They may be further refined, usually with lime and activatedclay, to remove any deleterious byproducts, if present. Further, thesulpho-halogenated monoesters may be blended with mineral lubricatingoils to obtain various compounded lubricants; the sulpho-halogenatedmonoesters being sometimes mixed with mineral oil prior to suchrefining. That is, the present invention achieves various improvementsin making sulphohalogenated monoesters and utilizing them in lubricantsand other compositions, the recovery of valuable glycerine being one ofthe advantageous features of this invention.

The manufacture of sulpho-halogenated monoesters of fatty acids and oflubricating oil compositions containing such sulpho-halogenated estersare well known. For instance, in Patent 2,179,062 to Smith and Cantrell,they have described and claimed improved lubricants comprising a mineraloil lubricating base and a minor amount of sulpho-chlorinatedmonoesters. As there shown, such lubricants have many advantageousproperties and uses.

In that patent, Smith and Cantrell have specifically claimed lubricantscontaining sulphochlorinated sperum oil and like monoesters,particularly improved motor oils and like lubricants which areadvantageous in lubricating cadmiumsilver and other special alloybearings without corroding said alloy bearings. As there pointed out,sperm oil, although often termed a fatty oil, is quite different fromthe ordinary fatty oils whcih are esters of glycerine, sperm 011 beingcomposed principally of fatty esters of monohydric alcohols. Further,the monoesters of sperm oil contain unsaturated aliphatic groups and arecapable of reacting with sulphur chlorides to form simple additionproducts which are substantially neutral and are advantageousimprovement agents for use in lubricating compositions. The superiorityof such sulpho-halogenated monoesters, as a class, in making improvedlubricants, is fully shown in Patent 2,179,062.

As disclosed and described in that patent, such sulpho-halogenatedmonoesters of fatty acids can be easily prepared by sulpho-halogenatingunsaturated fatty or aliphatic esters having the formula R-(fi-O-Rwherein R and R represent straight chain aliphat c groups, at least oneof said groups being unsaturated. In the methods there described,

the said monoesters are reacted with sulphurv 2 a,sco,oos

' exothermic heat of reaction. With the temperature maintained between50 and 90' I". while the sulphur chloride is vigorously combining withthe sperm oil, particularly good results were obtained. In such methodsnaturally occurring monoesters, such as sperm oil, etc. are ordinarilyemployed, as shown in Patent 2.179.062. However, as disclosed in thatpatent. synthetic unsaturated aliphatic monoesters, such as obtained byesterifying suitable fatty acids with appropriate alcohols, may likewisebe reacted with sulphur chlorides to produce sulpho-chlorinatedmonoesters.

We have now-found that such sulpho-halogenated monoesters of fatty acidscan be prepared advantageously from glycerides of unsaturated fattyacids, such as fatty oils or mixture of such fatty oils, by new andimproved methods yielding glycerine as a valuable byproduct, as well asexcellent sulpho-halogenated monoesters useful in improving minerallubricating oils and lubricants. As is well known, most fatty oils andfats are complex mixtures of fatty glycerides, their main constituentsbeing triglycerides. Generically, these triglycerides may be representedby the following formula:

wherein R represents the aliphatic group of a fatty acid which may besaturated or unsaturated. On the other hand, the main distinctionbetween fats (solid glycerides) and fatty oils (liquid glycerides) isthat the former, are mostly glycerides of saturated acids, whereas thelatter are mostly glycerides or unsaturated fatty acids. For instance,stearin, which is the main constituent of many fats, is the triglycerideof stearic acid. On the other hand, olein, which is the main constituentof many fatty oils, is the triglyceride ofoleic acid, a fatty acidcontaining one double bond in the aliphatic chain thereof. For instance,lard oil contains substantial amounts of oiein. This particularglyceride is also present in many other fatty oils, particularly thevegetable oils. However, vegetable oils also contain glycerides of otherfatty acids, including fatty acids containing two or three double bondsin the aliphatic chain, such as linoleic,

linolenic and similar acids. In fact, many oils contain substantialamounts of mixed fatty glycerides wherein the hydroxyl groups of theglycerlne are esterified with different fatty acids, the three hydroxylgroups being sometimes esterified oils and mixtures thereof according toour imthen convert these sulpho-chlorinated glycerides into the desiredsulpho-chloro-monoesters by reaction with monohydric alcohols, usuallyin the" presence of a catalyst such as sulphuric acid. Thesulpho-chloro-monoesters so obtained are separated from the glycerineand may be further refined, if desired. Likewise, the separated glycournew methods.

erine is' recovered and may also be refined as desired. I In this way weobtain valuable glycerine as a byproduct, as well as desirablesulpho-chloro-monoesters, both products being high grade materials.

In preparing the sulpho-chlorinated fatty glycerldes, a wide variety offatty oils or other glycerides of unsaturated fatty acids may beemployed. In general, any fatty glyceride containingat least one mole ofunsaturated fatty acid is useful in the present processes; triglyceridescontaining two or three moles of unsaturated fatty acids are alsoadvantageous.

In particular, we find that fatty oils having iodine numbers rangingfrom 50 to 200 can be readily reacted with sulphur chlorides and thenconverted into sulpho-chloro-monoesters which are particularlyadvantageous improvement agents for lubricating oils. For example, lardoil having an iodine number of approximately '72 yields advantageousproducts when processed by While lard oil contains substantial amountsof oiein as the main constituent thereof, it also contains varyingamounts of glycerides of other fatty.acids, some saturated and "someunsaturated, and the final product obtained 40 from it is a mixture ofmonoesters of such acids,

with three different acids, respectively. Likewise,

many fats also contain mixed glycerides, varying amounts of unsaturatedfatty acids being present in addition to saturated fatty acid. Suchmixed glycerides, upon hydrolysis, yield two or three different fattyacids. That is, ordinarily fats and fatty oils are not simple glyceridesof a single fatty acid. Instead, they usually contain varying amounts ofmixed glycerides, in addition to may be obtained by processingcommercial fat y the sulphur and chlorine being added to the double bondof the unsaturated fatty acid. However, the final products obtained fromlard oil contain relatively large amounts of monoesters ofsulfo-chlorinated oleic acid. In fact, olein is typical of theglycerides of unsaturated fatty acids which are particularly useful andadvantageous in the present processes?- Moreover, we may also employwithadvantage, other glycerides and mixtures of glycerides having iodinenumbers ranging from '70 to 120, many of the commercial fatty oilshaving iodine numbers within this range. Other glycerine mixtures havingiodine numbers within this range can be readily prepared by blendingtogether various fatty oils. For instance, lard oil may be blended withother fatty oils, such as cottonseed oil, menhaden oil, soybean oil,corn oil, and other oils having relatively high iodine numbers andcontaining glycerides of fatty acids carrying two or three double bondsin the aliphatic chain thereof. That is, by selecting the fatty oilsemployed, or blending together various fatty oils or both, finalproducts comprising mixtures of sulpho-chloro-monoesters and havingparticularly advantageous properties can be readilyobtained.

Such fatty oils or oil mixtures containing glycerides of unsaturatedfatty acids may be reacted with any of the usual sulpho-chlorides suchas.

sulphur monochloride (SaClz) sulphur dichloride (SO12), etc. or mixturesthereof. Ordinarily, the commercial sulphur chlorides are used in thegeneral practice of our invention. Substantially puresulpho-monochloride has a light yellow color. The usual'commercialsulpho-mono-chlorides are yellowish-red, heavy liquids. Commercialsulphur dichloride is a dark brownish-red liquid. However, mostcommercial preparations are more or less mixtures of various sulphurchlorides in equilibrium with each other. They are primarily composed ofsulphur dichloride and sulphur mono-chloride, depending upon thecommercial source of the preparation, and other sulphur chlorides, suchas sulphur tetrachloride (S014) and sulphur tri-tetrachloride (S3014)may also be present. Commercial sulphur chloride preparations having thefollowing properties may be employed in the practice of this invention:

Specific gravity, /15 C 1.6 to 1.7 Melting point C 78 to 80 Boilingrange C..- 59 to 139 Color Light yellow to dark red Sulphur per cent31.1 to 47.4 Chlorine do 68.9 to 52.6

That is, any of the commercial sulpho-chloride preparations are usefulfor the present purposes, and by selecting a particular sulphur chlorideor mixtures of sulphur chlorides, we can control the relative amounts ofsulphur and chlorine combined in the fattyoils and in thesulphochlorinated monoesters obtained therefrom.

As is well known, sulphur chloride, such as sulphur monochloride andsulphur dichloride, readidly react with fatty oils converting them intosulpho-chloro-glycerides. A- wide variety of sulpho-chlorinated productscan be obtained depending upon the reaction conditions employed. Ingeneral. we find that the sulpho-chlorinated products obtained byreacting 3 to 15 per cent of sulphur chloride by weight on the fatty oilare advantageous for the present purposes.

Further, we find it advantageous to employ certain controlled proceduresin reacting the fatty oils with the sulphur chloride. For instance, weprefer to effect this reaction at temperatures between and 180 F. withthe temperature maintained between and F., while the sulphur chloride isvigorously combined with th fatty oil, We obtain sulpho-chlorinatedglycerides which are particularly suitable for the present purposes. Inmaking such materials, any suitable cooling means may be employed andvigorous agitation is used to prevent overheating. To further hold thetemperature and reaction under control, the sulphur chloride isgradually added to the fatty oil; the rate of addition is such as willpermit the mixture to remain within the preferred temperature rangespecified, either with or without external cooling, despite the exo-"'v= thermic heat of reaction. If no special cooling means is provided,the addition of the sulphur chloride will ordinarily require from 2 to 5hours dependin upon the amount used and the other factor, an additionalperiod of 2 or 3 hours being allowed for the reaction to complete itselfafter all the said chloride has been added.

By adding the sulphur chloride to the lard oil or other fatty oil ormixture of oil, there is present during the initial reaction a largeexcess of the fatty glyceride. An excess of fatty oil is advantageousand favors the formation of simple addition products, while, at the sametime, restraining the formation of undesirabl side reaction productssuch as acid or acid-developing bodies, oil-insoluble products, etc.Further, any excess fatty oil remaining in the reaction mixture issubsequently converted into monoesters when the mixture is reacted withalcohol in the later stages of our processes, additional amounts ofglycerine being liberated and recovered. The alcohol esters of the fattyacids, so derived from the excess fatty oil, are also useful improvementagents in lubricants. In fact, such monoesters are frequently combinedwith mineral oils in producing compounded lubricants.

Thus, in the practice of the present invention,.

we sometimes use an amount of sulphur chloride insufficient tocompletely saturate the double bonds of all the fatty acids present inthe fatty oil. For instance, 3 to 15 per cent of sulphur chloride byweight on the fatty oil is satisfactory may readily control theproperties of the sulpho-- chlorinated fatty oils and the productsobtained therefrom, particularly their content of combined sulphur andchlorine, their viscosity, and other properties desired for the presentpurposes.

Generally, in making the sulpho-chlorinated fatty oils or glycerides,the reaction is so controlled as to primarily producesulpho-chloroaddition products and to prevent the formation of anysubstantial amount of hydrogen chloride or hydrogen sulphide or both.These sulphochloro-addition compounds or sulpho-chlorinated 'glyceridesare formed by saturating all or part of the double bonds of the fattyacid radicals with sulphur and chlorine. Accordingly, the amount ofsulphur chloride employed in this reaction does not exceed that requiredfor complete saturation of all of such double bonds; Usually we employsomewhat smaller amounts of sulphur than are necessary to satisfycompletely the unsaturation of the glycerides. In this way we cancontrol both the unsaturation and the content of sulphur and chlorine inthe sulphochlorinatd glycerides and in th final sulphochloro-monoesters.

In preparing the sulpho-chlorinated fatty glycerides, the fatty oils arereacted with the desired amount of sulphur chloride at controlledtemperatures, usually between 40 and F; This may be advantageously doneby preheating the fatty oil to about 300 F. until the water and othervolatiles are removed, cooling the sotreated oil to between 40-50 F.,and then gradually adding the sulphur chloride to the cooled oil, insmall doses, at such a rate that the temperature, without externalheating, is gradually increased to slightly below 100 F. by the time allthe sulphur chloride has been added. Th reaction mixture is thenmaintained at 90-100 F., by warming if necessary, until the reaction iscomplete. Then the reaction product is subjected to reduced pressure,usually about 100 mm. pressure, and heated to about C. to remove anytraces of unreacted sulphur chloride and volatile byproducts. Afterremoval of such volatiles, the sulpho-chlorinated glycerides are cooledusually to approximately room temperature. The sulpho-chlorinated fattyoils so obtained are liquid materials and can be readily converted intosulpho-chloro-monoesters, as more fully described post.

In converting the sulpho-chloro-glycerides into the correspondingmonoesters, the sulpho-chlorinated fatty oils are saponified andesterified with monohydric alcohols, the sulpho-chloroglycerldes beingreacted with an excess of the alcohol, usually in the presence of anacid catalyst. An advantageous catalyst is concentrated sulphuric acid,such as 85 to 105 per cent sulinto sulpho-chloro-monoesters, thestirring is discontinued and the mixture stratiiied into two layers, anupper ester layer and a lower glycerine layer. The two layers areseparated and may be refined as described post.

In forming the sulpho-chloro-monoesters, various alcohols may be reactedwith the sulphuchloro-glycerides and a wide range ofsulphqchloromonoesters obtained. 'Advantageous products can be preparedusing primary aliphatic alcohols, particularly the lower alkyl alcohols,such as methanol, ethanol, propanol, butanol and pentanol. Particularlygood products are obtained with pentanol. Likewise, other alcohols may.also be .used. For instance, branch-chain aliphatic alcohols, such asisopropanol,-isobutanol, etc. may be employed. Further, secondaryaliphatic monohydric alcohols may be used as well as primary alcohols.In general, any monohydric alcohol may be reacted with thesulphochloro-glyceride to form' useful sulpho-chloromonoesters andliberate the lycerine. After this reaction is complete, the reactionmixture is permitted to stratify into an upp r monoester layer and aglycerine layer. When sulphuric acid or other acid is employed as acatalyst in the reaction, the glycerine layer is somewhat acid and theseparated glycerine is usually further refined to obviate this aciditybefore recovering the glycerine.

After the sulpho-chloro-monoesters have been separated from theglycerine layer, they are usually further refined, advantageously byclay contacting. In this procedure an appropriate amount of activatedclay is added to the sulphochloro-monoesters, and the mixture isagitated until theclay absorbs the matter to be removed. Approximatelytwo pounds of fine activated clay per gallon of sour oil (monoesters) issufficient when the clay contacting is effected at elevatedtemperatures, say 275 F. The clay treated mixture is then filtered toremove the clay and other insolubles. To facilitate such removal, filteraids may be added to the mixture prior to filterin For this purposecommercial filter aids, such as Supercel, etc., are advantageous.Furthermore, in refining the sulpho-chloro-monoesters, it is sometimesadvantageous to treat them with lime to remove residual acid ty prior toclay contacting'. In such cases, the lime in excess of that necessary toobviate the mineral acidity may be added and the mixture stirred untilsubstantially neutral. The calcium salts and excess lime may be settledor filtered off prior to clay treatment. However, complete removal priorto clay treatment is not essential and, in many cases, the lime and claytreatment may be combined in one operation. In such combination refininga small amount of lime may be used, and the activated clay added to themixture after it is substantially neutral. Then all of the insolublesmay be removed in one operation by filter pressing.

In recovering and refining the'glycerine, the separated acid-glycerinelayer may be processsed in several ways. As statedante, this acid layeris usually neutralized with lime when sulphuric acid catalyst is used.In refining such byproduct glycerine, the glycerine also is mixed withan excess of hydrated lime, in the form of a slurry, and the mixtureagitated until substantially neutral. The so-treated glycerine is filterpressed to remove the calcium sulphate and excess lime. The recoveredglycerine is a high grade material. It may be further refined ifdesired. For instance, the filtrate may be vacuum distilled to recoversubstantially anhydrous glycerine. All of the various glycerinebyproducts obtained in these processes are useful per se for manypurposes.

From the foregoing description it will be evident that in the practiceof our invention many and various embodiments thereof may beemployed. Ingeneral, the several steps in our improved processes are interrelatedand correlated to obtain high grade sulpho-chlor'o-monoesters from fattyoils with recovery of useful byproduct glycerine. In the mainadvantageous embodiments thereof, our improved processes includereacting sulphur chloride with fatty oils containing glycerides ofunsaturated fatty acids to obtain sulpho-chloro-addition productsthereof, reacting the sulpho-chloro-glycerides with mono hydric alcoholin the presence of sulphuric acid to convert them intosulpho-chloro-monoesters, separating suchmonoesters from the glycerine,and refining the separated sulpho-chloro-monoesters usually with l meand clay. Likewise in recovering and refining the glycerine, the acidglycerine layer is heated with lime and otherwise refined to obtain pureglycerine. These and other embodiments of our invention are furtherillustrated in more detail by the specific examples givenpost.

The following examples are illustrative embodiments of the methods andproducts broadly set forth ante, and are not limitative of ourinvention.

EXAMPLE I This example illustrates one advantageous method of preparingsulpho-chloro-monoesters using commercial lard oil andsulpho-monochloride to produce sulpho-chloro-glycerides which arereacted with butanol; the lard oil and sulphomonochloride having thefollowing properties:

Commercial lard oil:

Specific gravity 0.915 solid fying point C 0 Saponification number195-196 Iodine No 56-74 Commercial sulphur monochloride (S2012):

Molecular weight 135.03 Specific gravity 1.678 Freezing point C Boi ingpoint C 135.6 Sulphur per cent 47.4 Chlorine do 52.6

The above commercial lard oil was a yellow semi-solid material obtainedfrom lard oil by cold pressing. The commercial monochloride was ayellowish red liquid having a penetrating odor. These materials werereacted together and processed as follows:

Into a suitable vessel, equipped with means for-agitating and forcooling and heating the mixture, there were charged 880 pounds of thelam on and then o8 pounds of the sulphur monociilorlde, gradually addedin small proportion over a period or two hours, the temperature of themixture being maintained at approximately 250 F. After all of thesulphur monoclnoride was added, the mixture was further agitated atapproximately 250 F. for 14 hours.

'1o the sulpho-chloro-glycerldes so obtained there were added 300 poundsof butanol contammg 1 per cent of 93 per cent sulphuric acid, and themixture agitated at 220 F. for 14 hours. Alter the reaction was completethe mixture was permitted to stratify into an upper ester and a lowerglycerme layer and the glycerine layer withdrawn.

The ester layer was then admixed with 5 pounds of lime and agitateduntil substantially neutral. The neutral mixture was then admixed with250 pounds of line activated clay (2 pounds of clay per gallon of souroil) and the mixture is agitated at 275 F. for 2 hours. After the claycontacting was completed, the mixture was filter pressed to remove theclay and other insolubles. The filtrate so obtained had the followingproperties Gravity, API 20.5 Viscosity, SUV:

210 F 42.4 Flash, OC F 380 Fire, 0C F 440 Pour F-.. +35 Sulphur percent-.. 5.57 Chlorine do.. 3.17

This filtrate was a mixture of butyl esters of the sulpho-chloro-fattyacids and was an excellent improvement agent for mineral lubricatingoils and lubricants.

EXAMPLE II This example illustrates one advantageous method of preparingsulpho-chloro-glycerides from commercial grades of lard oil and ofsulphur monochloride, commercial materials having the followingproperties being employed:

The above material were reacted together and processed as follows:

Into a suitable vessel equipped with means for agitating and for heatingand cooling the oil and reaction mixture, there were introduced 880pounds of the above lard oil and the oil was heated to 300 F. until anywater and other volatiles present were evaporated. Then the oil wascooled to approximately 50 F. and 106 pounds of the commercial sulphurchloride (approximately 12 per cent by weight on the oil) were graduallyadded. The rate of introducing sulphur chloride was so controlled as tomaintain the reaction temperature between 40 and r-.,theexotllermlc heator reaction being utilized to gradually bring the temperature to about90 F. when all the sulphur chloride had been added. it required about 2hours to so incorporate the sulphur chloride. 01 course, the tunerequired may be varied depending uponwhether or not external cooling isemployed. During this time, the reaction mixture wa vigorously agitatedto prevent any local overheating. After all the sulphur chloride hadbeen added, the reaction mixture was mamtamed at 90 to F. for a furtherperiod of 2 hours While the agitation was continued until the reactionwas substantially complete.

The hot sulpho-chiorinated oil product so obtained was subjected toreduced pressure of approximately 100 mm. and heated to F. under saidpressure to remove any unreacted sulphur chloride and other volatiles.After the volatiles were so removed, the sulpho-chlorinated glycerideswere cooled to approximately room temperature.

The sulpho-chlorinated lard oil so obtained had the followingproperties:

In the above example, the amount of sulphur chloride may be varied from6 to 14 per cent and other sulpho-chlorinated oils will be obtainedwhich have properties rendering them advantageous for the presentpurposes; the smaller percentages of sulphur chloride produced oilproducts having somewhat lower viscosities and higher gravities.Likewise other commercial sulphur chloride and fatty oils may beemployed, in making these sulpho-chlorinated glycerides. With thereaction temperature maintained between 50 and 100 F., we obtained fromany of the commercial fatty oils or mixtures of such oilssulpho-chlorinated oil products having good color and other properties.

The sulpho-chlorinated glycerides so obtained can be readily convertedinto sulpho-chloromonoesters by reacting them with an excess ofmonohydric alcohol. For instance, excellent sulpho-chloro-monesters areobtained by reacting the sulpho-chlorinated glycerides with butylalcohol.

In making butyl esters from the above sulphochloro-glycerides, 300pounds of the sulphochlorinated lard oil were admixed with 85 pounds ofacidulated butyl alcohol, prepared by mixing 15 pounds of 96 per centsulphuric acid with 70 pounds of butanol. This reaction mixture wasagitated and gradually heated to 220 F. in approximately 1 hours, andthen maintained at this temperature for 4 hours while continuing theagitation. After the reaction was completed the stirring wasdiscontinued and the mixture stratified into an ester layer and aglycerine-acid layer. The glycerine layer was withdrawn and 358 poundsof the sulpho-chloromonoesters so-obtained were admixed with 15 6aseopoc pounds of lime and 40 pounds of activated clay and the mixturemaintained at 275 F. with agitation for 3 hours. After this claycontacting, the sulpho-chloro-monoesters were filter pressed to removethe clay and other insoluble matter. The filtrate was an excellentimprovement agent for mineral oils and lubricants.

The separated glycerine-acid layer weighed to remove the insolubles suchas sulphate and 'ex- Table 1 Alcohol used for esterlflcation ButanolMethanol Isopropanol Clay-treated sulphoehloromonoestcrs:

Gravity A?! mi 22.4 23 2 Viscosity, SUV, sec- 110 109 102 210 F.... 42.441. 2 36. 3 Flash. F 380 390 380 Fire, 00, F 440 445 440 Sui bur, B, percent 5.6 6. i 6.8 Ch orine, per oant..-.--.- 3. 2 3. 5 3.3

The sulpho-chloro-monoester compositions given in the above table aremerely illustrative of, certain embodiments of this invention, and otheralcohol esters of sulpho-chloro-fatty acids can be prepared in likemanner from other fatty oils, particularly those containing glyceridesof unsaturated fatty acids.

Likewise, mixtures of fatty oils may be employed in our processes; two'or more fatty oils being blended together to obtain mixtures of fattyglycerides advantageous for the present purposes. As stated ante,advantageous sulphochloro-monoesters can be obtained from fatty oils andmixtures of oils having an iodine number between 70 and 120. 3

Also, mineral oils, such as the usual grades of lubricating oils, may beincorporated with the sulpho-chloro-monoesters during the processing.Suchoils may be advantageously'admixed with the"sulpho-chloro-monoestersprior to clay refining. In this way concentrates or lubricants can bedirectly obtained from the refining operations. The presence of themineral oil facilitates precipitation and removal of byproducts whichare insoluble in the final lubricant. For instance, in the embodimentsillustrated in Examples I and II ante, varying amounts of minerallubricating oil, advantageously a Pennsylvania base neutral oil, havinga viscosity of '10 SUV at 100 F., may be readily incorporated prior tothe clay treatment; and the mineral oil solution of thesulpho-chloro-monoesters then. refined with clay to produce concentratedsolutions, which are good lubricants and are useful to produce otherlubricants containing small amounts of these improvement agents. We haveprepared a large number of such mineral oil compositions in accordancewith this invention and the make-up and properties of a few of them aregiven in the following Table II:

Table II A Pennsyi- A Penna lvania typo vania tyge A ax at??? 1 b ri t ucan Description coigyinlngt oogigning gafg fl 0 maniac: inhibitor gdescribed escri ante ante m- 6 Q a. 8 22- I 4% 1, 537 510 w I!) 56 455535 406 B25 B06 400 0 -5 l0 3. 5 4. 0 4- I The above compositions areexcellent motor oils. Other improved lubricants can also be readilyprepared, such as lubricants for automobile gears. In fact, excellentautomobile gear lubricants can be made by incorporating from 5 to 10 percent by weight of these sulpho-chloromonoesters in a suitable base oil.

In general, sulpho-chloro-monoesters containing from 3.0 to 8.0 per centof combined chlorine, by weight, are excellent improvement agents formineral lubricating oils and lubricants and such advantageousimprovement agents may be readily prepared by the present invention fromglycerides of unsaturated fatty acids such as commercial fatty oils ormixtures thereof, with recovery of useful by-product glycerine.

According y. in the broad practice of the present invention, in additionto the specific embodiments that are given ante, other and diflerentembodiments within its generic scope may be employed.

What we claim is:

1. In the manufacture of sulpho-chloro-monoesters, the improvement whichcomprises reacting a sulpho-chlorinated fatty glyceride with amonohydric aliphatic alcohol acidified with sulphuric acid to completelyliberate the glycerine from said glyceride and to convert the same into,sulphochloro-fatty monoesters of said alcohol, and separately recoveringthe sulpho-chloro-monoesterl and the glycerine so obtained.

neutral glycerine is filtered to remove the excessof lime and otherinsoluble matters.

4. The process of claim 2 wherein the sulphociiloro-monoesters arerefined with activated c ay.

5. In the manufacture of sulpho-chloro-monoesters, useful as improvementagents for mineral lubricating oils and lubricants, the improved processwhich comprises reacting sulphur chloride with a fatty 011 containinggiycerides of unsaturated fatty acids to form sulpho-chlorinated fattyglycerides and then converting said sulphochlorinated fatty glyceridesinto sulpho-chlorinated fatty monoesters by reacting thesulphochlorinated fatty oil with a monohydric aliphatic alcoholacidified with sulphuric acid to saponify the sulpho-chlorinated fattyglycerides and convert the same into sulpho-chlorinated fatty monoestersof said alcohol, separating the glycerine so liberated from saidgiycerides, and recovering and refining the sulpho-chlorinated fattymonoesters so produced to obtain substantially neutralsulpho-chlorinated monoesters useful as improvement agents for minerallubricating oils and lubricants.

6. The process of claim wherein said sulphur chloride is sulphurmonochloride.

7. The process of claim 5 wherein said sulphur chloride is sulphurdichloride.

8. The process of claim 5 wherein said fatty oil is a non-drying oil.

9. The process of claim 5 wherein said fatty oil is lard oil. 1

10. Th process of claim 5 wherein said fatty oil comprises a mixture oflard oil and fatty oils having an iodine number greater than 130, themixed oils having an iodine number between '70 and 120.

11. The process of claim'5 wherein said fatty oil has an iodine numberbetween and 120.

12. In the manufacture of sulpho-chloro-monoesters from fatty oils andmixtures of fatty oils having an iodine number between 70 and andcontaining glycerides of unsaturated fatty acids, the improved processwhich comprises reacting such fatty Oils with sulphur chloride to formsulpho-chloro-addition products, reacting the sulpho-chlorinated fattyoils with a, monohydric aliphatic alcohol in the presence of sulphuricacid to form sulpho-chloro-monoesters and liberate glycerine, separatingthe acid glycerine from the sulpho-chloro-monoesters, refining theseparated sulpho-chloro-monoesters by contacting with activated clay andseparating the refined sulphochloro-monoesters from the clay.

13. The process of claim 12 wherein the separated glycerine isneutralized with an excess of lime and the neutral glycerine isseparated from the excess lime and other insoluble matter.

HERSCHEL G. SMITH. TROY L. CANTRELL. JOHN G. PETERS.

